water

Article
Removal of Hardness from Water Samples by a
Carbonation Process with a Closed Pressure Reactor
Min Kyung Ahn 1 , Ramakrishna Chilakala 2 , Choon Han 3 and Thriveni Thenepalli 2, * ID

1 Ewha Girls High School, 26 Jeongdong-gil, Jung-gu, Seoul 04516, Korea; mkahn12@naver.com
2 Carbon Mineralization Center, Climate Change Mitigation and Sustainability Division, Korea Institute of
Geosciences and Mineral Resources (KIGAM), 124, Gwahak-ro, Yuseong-gu, Daejeon 34132, Korea;
ramach2008@yahoo.com
3 Chemical Engineering Department, Kwangwoon University, 20 Kwangwoon-ro, Nowong-gu,
Seoul 01897, Korea; chan@kwangwoon.ac.kr
* Correspondence: thenepallit@rediffmail.com; Tel.: +82-42-868-3578

Received: 15 November 2017; Accepted: 8 January 2018; Published: 10 January 2018

Abstract: One of the undesirable characteristics of some ground and natural water sources is
hardness. Hard water can cause many problems around the world, including increased scaling
on water pipes, boilers, atopic eczema and odd-tasting drinking water. Hardness in natural water
is caused by dissolved minerals, mainly calcium and magnesium compounds. According to the
Water Quality Association (WQA) and the United States Geological Survey (USGS), hard water
is classified based on the Ca2+ and Mg2+ ion concentration in waters, as follows: 0–60 ppm as
soft; 61–120 ppm as moderately hard; 121–180 ppm as hard and more than 180 ppm as very hard
water. Most water utilities consider a hardness level between 50 and 150 ppm of CaCO3 as publicly
acceptable. The present study investigated the effects of a carbonation process on the removal of
hardness in different water samples. Currently, a wide variety of hardness removal technologies are
available. Among those conventional methods, carbonation is an inexpensive process which can be
used for the removal of Ca2+ and Mg2+ ions from hard water. This study measured the hardness
levels of 17 different water samples using the ethylene diamine tetra acetic acid (EDTA) method.
Among these, Seoul outdoor swimming pool water (140 ppm) samples showed high concentrations
of Ca2+ and Mg2+ ions. The hardness of the different water samples was reduced by 40–85% by a
carbonation process with a closed pressure reactor for a 5 min reaction time.

Keywords: water hardness; removal; carbonation; closed pressure reactor

1. Introduction
Hardness (hard water) is one of the common water quality problems throughout the world.
A total of 70% of the earth’s surface is covered by water. Of this, 97% is only sea water (non-drinkable).
Only 2.5% of fresh water is accessible for human use and of this only 0.5% is used as drinking water.
Hard water is found at a rate exceeding 85%, as water picks up minerals such as magnesium and
calcium ions from rocks and soil, leading to the hard water. Ground water contains more minerals
than surface water, so it is harder than surface water. There are many exceptions, i.e., lakes in lime
soil districts [1]. Knowing the hardness of water is important when evaluating its use as a domestic
or industrial water supply. Hard water interferes with laundering, washing, bathing and personal
grooming [2]. Clothes laundered in hard water may look dingy and harsh. Hard water utilization in
the home can lead to other issues as well. It also affects soap and detergent used for cleaning because
soap used in hard water combines with the high amount of minerals to form a sticky sludge. Bathing
with soap in hard water can deposit this sticky residue onto the skin and can lead to irritation under
slightly acid conditions.

Water 2018, 10, 54; doi:10.3390/w10010054 www.mdpi.com/journal/water

Water 2018, 10, 54 2 of 10

Water 2018, 10, 54 2 of 10

Several studies have indicated a link between hardness concentrations (particularly calcium and
magnesium) Several
andstudies have indicated
cardiovascular a link between
diseases, hardness
Alzheimer’s concentrations
disease (particularly
and atopic eczema calcium and
[3,4]. However,
the link is tenuous, and many confounding variables exist in the studies [5]. Hard water isthe
magnesium) and cardiovascular diseases, Alzheimer’s disease and atopic eczema [3,4]. However, mainly
link is tenuous, and many confounding variables exist in the studies [5]. Hard water is mainly caused
caused by calcium and magnesium cations and to a lesser extent aluminum, iron and other cations.
by calcium and magnesium cations and to a lesser extent aluminum, iron and other cations. Calcium
Calcium and magnesium are the two major cations responsible for hardness in natural water [6].
and magnesium are the two major cations responsible for hardness in natural water [6]. Therefore,
Therefore,
for mostforwaters,
most waters,
the totalthe total hardness
hardness is caused
is caused by by major
major cations and cations and
associated associated
anions anions
as shown in as
shown in Figure
Figure 1. 1.

Figure 1. Major cations and associated anions in water.

Figure 1. Major cations and associated anions in water.
The cations are usually associated with the anions of HCO3−, CO32− and OH− alkalinity ions and
The cations are usually
acidity-associated associated
ions such as SO42−, with
NO3−, the
andanions
Cl−. Carbonate − , CO 2−
of HCO3hardness andto OH − number
alkalinity
of ions
3 refers the
hardness ions associated with 2
alkalinity −ions. −
When the −
solution is super-saturated,
and acidity-associated ions such as SO4 , NO3 , and Cl . Carbonate hardness refers to the numberthe cations in the
water can
of hardness ionsprecipitate
associatedas with
a hard scale. Carbonate
alkalinity ions. When hardness is sensitive
the solution to temperature and
is super-saturated, thecancations
precipitate easily. At high temperatures, Mg salts can also produce hard scales in boilers.
in the water can precipitate as a hard scale. Carbonate hardness is sensitive to temperature and can
The main objective of this study is to describe the removal of hardness in water by a carbonation
precipitate easily. At high temperatures, Mg salts can also produce hard scales in boilers.
process in a closed-pressure reactor. In this paper, the crystallization process of precipitated calcium
The main objective of this study is to describe the removal of hardness in water by a carbonation
carbonate (PCC) and magnesium carbonate from hard water samples were investigated. The calcite
process
PCCinthus
a closed-pressure
obtained couldreactor. In this
be utilized as apaper, the crystallization
filler material to enhance theprocess of precipitated
mechanical propertiescalcium
of
carbonate (PCC) and magnesium carbonate from
composites in the plastics and paper industries. hard water samples were investigated. The calcite
PCC thus obtained could be utilized as a filler material to enhance the mechanical properties of
2. Materials
composites in theand Methods
plastics and paper industries.
The existence of Ca2+ and Mg2+ ions in water causes hardness. A water supply with a hardness
2. Materials and Methods
level of 100 parts per million (100 ppm) contains the equivalent of 100 g of CaCO3 in one liter of water.
The total
The hardness
existence is 2+
of Ca equal the2+
andtoMg sum
ionsof in
magnesium hardness
water causes and calcium
hardness. hardness.
A water supply with a hardness
level of 100 parts per million (100 ppm) contains the equivalent of 100 g of CaCO3 infor
In the present experiment, total hardness was measured by the EDTA method onehard water
liter of water.
samples collected from different areas of South Korea and artificial hard water samples that were
The total hardness is equal to the sum of magnesium hardness and calcium hardness.
prepared in the lab. The hardness was then reduced by the carbonation process. In all, five different
In the present experiment, total hardness was measured by the EDTA method for hard water
artificial hard water samples, five different drinking water samples, and eight different natural water
samples collected from different areas of South Korea and artificial hard water samples that were
samples were tested, as shown in Table 1.
prepared in the lab. The hardness was then reduced by the carbonation process. In all, five different
artificial hard water samples, Tablefive different
1. Different drinking
water samples water samples,
names with and eight different natural water
given numbers.
samples were tested, as shown
Artificial Hard Water in Table 1.
Drinking Water Natural Water
Sample Name Number Sample Name Number Sample Name Number
CHOICE
1. Different water samples
Artificial Soft water TableA-(1) D-(1) names with given
Softenernumbers.
pass water N-(1)
water
Artificial Slightly Hard
Artificial Hard Water
A-(2) ViO water Drinking
D-(2) Water Seoul Arisu waterNatural Water N-(2)
water
Sample Name
Artificial Moderately Number Sample
Sam Da Soo Name Number Sample Name Number
A-(3) D-(3) Seoul Park Tap water N-(3)
Hard water
Artificial Soft water A-(1) waterCHOICE water D-(1) Softener pass water N-(1)
Artificial
Artificial VeryHard
Slightly Hardwater
A-(4) A-(2) ViO water
O-EAU water D-(4) D-(2) Seoul Arisu
Seoul Outdoor Swimming water
pool (1) water N-(2)
N-(4)
water
Sam Da Soo
Artificial Moderately Hard water A-(3) D-(3) Seoul Parkpool
Seoul Outdoor Swimming Tap water
(2) water N-(3)
N-(5)
water
Seoul Outdoor Swimming pool Toilet
Seoul Outdoor N-(6)
Artificial Very Hard water A-(4) O-EAU water D-(4) water Swimming pool N-(4)
(1) water
(Korea Institute of Geoscience and
Seoul Outdoor Swimming pool N-(7)
Mineral Resources(KIGAM)-Waste water N-(5)
(2) water
Seoul Outdoor Swimming pool
N-(6)
Toilet water
(Korea Institute of Geoscience
and Mineral N-(7)
Resources(KIGAM)-Waste water
Water 2018, 10, 54 3 of 10
Water 2018, 10, 54 3 of 10
2.1. Artificial Hard Water Samples
Synthetic artificially hard water was prepared with major ions mixed into the proper amounts
2.1. Artificial Hard Water Samples
of fresh water. Most compositions include Mg2+, Ca2+, Na+, K+ and Cl−, SO42− depending on their
Synthetic
hardness and on artificially
the user hard water was
requirements. prepared
CO withat
32− is present major ions mixed intointhe
low concentrations proper
most amounts
natural water
of fresh water. Most compositions include Mg 2+ , Ca2+ , Na+ , K+ and Cl− , SO 2− depending on their
samples at a pH of seven. The alkalinity was measured frequently for the soft 4 and hard water and
hardness
was and on
assumed to the user requirements.
be equal CO3 2− isofpresent
to the concentration the HCO at low concentrations
3− ions in mostartificial
[7]. The different natural water
samples at a pH
were of seven.
denoted The alkalinity
as soft, was moderately
slightly hard, measured frequently
hard and for the
very softwater
hard and hard
withwater and
respect towas
the
assumed to be equal to the concentration of the HCO − ions [7]. The different artificial water samples
chemical compositions [8], as shown in Table 2. 3
were denoted as soft, slightly hard, moderately hard and very hard water with respect to the chemical
compositions [8], as shown
Table in Table composition
2. Chemical 2. for the preparation of hard water.
Water Samples Reagent Added (mg/L) Approximate Final Water Quality
Table 2. Chemical composition for the preparation of hard water.
NaHCO3 CaSO4·2H2O MgSO4 KCl pH Hardness (mg/L)
Soft
Water Samples
12.0 7.5
Reagent Added (mg/L)
7.5 0.5 Approximate
6.4–6.8 Final Water Quality
10–13
Slightly hard 48.0 3
NaHCO 30.0
CaSO4 ·2H2 O MgSO4 30.0 KCl2.0 7.2–7.6
pH 40–48
Hardness (mg/L)
ModeratelySofthard 96.0
12.0 7.560.0 7.5 60.0 0.54.0 6.4–6.8
7.4–7.8 10–1380–100
Hard
Slightly hard 192.0
48.0 120.0
30.0 120.0
30.0 2.08.0 7.2–7.6
7.6–8.0 160–180
40–48
Moderately hard 96.0 60.0 60.0 4.0 7.4–7.8 80–100
Very hard Hard 384.0
192.0 240.0
120.0 240.0
120.0 16.0
8.0 8.0–8.4
7.6–8.0 280–320
160–180
Very hard 384.0 240.0 240.0 16.0 8.0–8.4 280–320

2.2. Water Hardness as Measured by the EDTA Method

2.2. Water Hardness as Measured by the EDTA Method
Water hardness can be readily determined by titration with the chelating agent EDTA (ethylene
Water
diamine hardness
tetra acetic can be readily
acid). In the determined
sample solutionby titration with the
containing chelating
calcium and agent EDTA (ethylene
magnesium ions, the
diamine tetra acetic acid). In the sample solution containing
reaction takes place with an excess of EDTA by a titration process calcium and magnesium ions, the reaction
the indicator added remains
takes
as place withblack
eriochrome an excess of EDTA by
T (EBT)-blue a titration
because all ofprocess
the Caand
2+ theMg
and indicator
2+ ions added
presentremains as eriochrome
are complexed with
black
the T (EBT)-blue
EDTA because
[9]. During this process, Ca2+
all of thethe and Mg
EDTA 2+ ions present are
reacts with the Ca2+ and complexed
Mg2+ ions with
andtheto EDTA [9].
form the
During this process, the EDTA reacts with the Ca 2+ and Mg2+ ions and to form the EDTA-Ca and
EDTA-Ca and EDTA-Mg complex (Figure 2), and after the completion of this reaction, the wine red
EDTA-Mg
color complex
disappears (Figure
slowly 2), andthe
because after the completion
EBT-Ca and EBT-Mgof this
arereaction,
replaced theand
wine redCa-EDTA
form color disappears
stable,
slowly because the EBT-Ca and EBT-Mg are replaced and form Ca-EDTA stable, colourless
colourless complex, while simultaneously a blue color appears due to the effect of the EBT indicator complex,
while
[10]. simultaneously a blue color appears due to the effect of the EBT indicator [10].

Figure 2. EDTA
Figure complex
2. EDTA complexformation
formation by thereaction
by the reactionwith
withCaCa
2+ and Mg
2+ and 2+ ions.
Mg2+ ions.

2.3.
2.3. The
The KIGAM
KIGAM Closed
Closed Pressure Reactor for
Pressure Reactor for aa Carbonation
Carbonation Process
Process
The Korea Institute
The Korea Institute of
of Geosciences
Geosciences and and Mineral
Mineral resources
resources (KIGAM),
(KIGAM), hashas introduced
introduced aa closed
closed
pressure reactor for the removal of hardness. This can be accomplished in conjunction
pressure reactor for the removal of hardness. This can be accomplished in conjunction with the with the
coagulation
coagulation of
of suspended
suspended solids,
solids, as
as shown
shown inin Figure
Figure 3.3. Here,
Here, aa 11 L
L closed
closed pressure
pressure reactor,
reactor, with
with aa
maximum working CO 2 pressure of 10 bar is used. It is connected with a CO2 cylinder containing
maximum working CO2 pressure of 10 bar is used. It is connected with a CO2 cylinder containing 60 L
60 L of carbonated
of carbonated water,
water, as shownas in
shown
Figurein4. Figure 4. This
This closed closedreactor,
pressure pressure reactor,
based uponbased upon a
a carbonation
carbonation
process, process,
is used is used
to control thetoconcentrations
control the concentrations
of calcium and of magnesium
calcium andionsmagnesium ions inInhard
in hard water. this
water.
carbonation process, 1 L of each water sample was brought into the reactor chamber and chamber
In this carbonation process, 1 L of each water sample was brought into the reactor CO2 gas
and CO2 gas was injected using a CO2 injector machine. The closed pressure reactor has two
Water 2018, 10, 54 4 of 10

wasWater 2018, 10,

injected 54
using a CO2 injector machine. The closed pressure reactor has two alternative outlets 4 of 10for
Water 2018, 10, 54 4 of 10
collecting the final precipitated solution. The upper outlet is for the bench scale reactor (1–2 L) and the
alternative outlets for collecting the final precipitated solution. The upper outlet is for the bench scale
bottom outletoutlets
alternative is for the pilot scalethe
for collecting reactor.
final precipitated solution. The upper outlet is for the bench scale
reactor (1–2 L) and the bottom outlet is for the pilot scale reactor.
During
reactor (1–2 the
L)hard
and thewater carbonation
bottom outlet isprocess by the
for the pilot closed
scale pressure reactor, three different CO2 flow
reactor.
During the hard water carbonation process by the closed pressure reactor, three different CO2
During
rates were the hard
injected, givingwater carbonation
different reactionprocess
times. by
Thethe closedinvolved
process pressure7reactor,
g/L COthree
2 for adifferent CO2
3 min reaction,
flow rates were injected, giving different reaction times. The process involved 7 g/L CO2 for a 3 min
14 flow
g/L ofrates
COwere gas injected,
for a 4 mingiving different
reaction and 21reaction
g/L oftimes.
CO2 forThea process involvedThe
5 min reaction. 7 g/L CO2 for a 3reaction
carbonation min
reaction, 142 g/L of CO2 gas for a 4 min reaction and 21 g/L of CO2 for a 5 min reaction. The carbonation
2+The 2+ ions to
reaction,
began with 14
theg/L of CO2 gasoffor
hydration a 4 min
carbon reaction
dioxide inand
the 21 g/L ofwhich
water, CO2 for a 5 minwith
reacted reaction.
Ca and carbonation
Mg
reaction began with the hydration of carbon dioxide in the water, which reacted with Ca2+ 2+ and Mg2+
reaction
form calcium began with the
carbonate hydration
and magnesiumof carbon dioxide
carbonate in the water,
precipitates. Thewhich reacted
effects of thewith Ca dioxide
carbon and Mgflow2+
ions to form calcium carbonate and magnesium carbonate precipitates. The effects of the carbon
ions
rate, thetotemperature
form calciumatcarbonate and and
carbonation, magnesium
the pH on carbonate
thethe precipitates.
precipitation The effects
formation of the
were carbon
investigated.
dioxide flow rate, the temperature at carbonation, and pH on the precipitation formation were
Thedioxide flow
pH values of rate, the
all pH temperature
the samples at carbonation, and the pH on the precipitation formation were
investigated. The values ofwere measured
all the samplesbefore
were carbonation and after
measured before the carbonation
carbonation and afterprocess
the
investigated.
with a pH meter The pH values
(A 214, Orion, of all theScientific,
samples were measured USA).
before carbonation and after the
carbonation process with a pHThermo
meter (A 214, Orion, Waltham,
Thermo MA,Scientific, Waltham, MA, USA).
carbonation process with a pH meter (A 214, Orion, Thermo Scientific, Waltham, MA, USA).

Figure 3. Carbonation process

process with the closed pressure reactor.
Figure3.3.Carbonation
Figure with the
Carbonation process with theclosed
closedpressure
pressurereactor.
reactor.

Figure 4. KIGAM bench scale carbonation reactor.

Figure4.4.KIGAM
Figure KIGAM bench
bench scale
scale carbonation
carbonationreactor.
reactor.
2.4. Characterization of Crystals by SEM, XRD and EDS
2.4. Characterization of Crystals by SEM, XRD and EDS
2.4. Characterization of Crystals by SEM, XRD and EDS
The crystallites formed join together to form polycrystalline particles with a rhombohedral
The crystallites formed join together to form polycrystalline particles with a rhombohedral
shape. Re-crystallization
The crystallites formedtakes
join place on the
together surface
to form of the particles
polycrystalline to createwith
particles a very thin single-crystal
a rhombohedral shape.
shape. Re-crystallization takes place on the surface of the particles to create a very thin single-crystal
shell, which thentakes
Re-crystallization extends
placeinwards,
on the leading of
surface tothe
true single crystals.
particles to create Figure
a very 5a shows
thin the scanning
single-crystal shell,
shell, which then extends inwards, leading to true single crystals. Figure 5a shows the scanning
electron
which microscopy
thenmicroscopy (SEM)
extends inwards, (JEOL Company, Seoul, South Korea) results of the rhombohedral
electron (SEM) leading to true single
(JEOL Company, crystals.
Seoul, South Figure
Korea) 5a showsofthe
results thescanning electron
rhombohedral
calcium carbonate
microscopy (SEM) crystals
(JEOL and Figure
Company, Seoul, 5b shows
South the results
Korea) X-ray diffraction
of the (XRD) (Korea
rhombohedral Institute
calcium of
carbonate
calcium carbonate crystals and Figure 5b shows the X-ray diffraction (XRD) (Korea Institute of
Geosciences
crystals and Mineral
and Figure 5b shows Resources
the X-ray (KIGAM), Daejeon,
diffraction South
(XRD)South
(KoreaKorea) analysis,
Institute which indicated
of Geosciences that
and Mineral
Geosciences and Mineral Resources (KIGAM), Daejeon, Korea) analysis, which indicated that
pure
Resourcescalcite was
(KIGAM), formed. The
Daejeon, magnesium
South Korea) carbonate
analysis,peak
whichdid not appear in the XRD results due to a
pure calcite was formed. The magnesium carbonate peak did indicated
not appearthat pure
in the XRD calcite was
results dueformed.
to a
low quantity of magnesium, but the energy dispersive x-ray spectroscopy (EDS) (Korea Institute of
The magnesium
low quantity ofcarbonate
magnesium,peakbutdidthe
notenergy
appeardispersive
in the XRD results
x-ray due to a low
spectroscopy quantity
(EDS) (KoreaofInstitute
magnesium,
of
Geosciences and Mineral Resources (KIGAM), Daejeon, South Korea) results show a negligible
butGeosciences
the energyand dispersive
Mineral x-ray spectroscopy
Resources (KIGAM),(EDS) (Korea
Daejeon, Institute
South Korea)ofresults
Geosciences
show a and Mineral
negligible
quantity of magnesium.
Resources
quantity(KIGAM), Daejeon, South Korea) results show a negligible quantity of magnesium.
of magnesium.
Water 2018, 10, 54 5 of 10
Water 2018, 10, 54 5 of 10

(a) (b)
Figure5.5.(a)(a)
Figure SEMSEM
and and EDS results
EDS results of calcium
of calcium and magnesium
and magnesium carbonate
carbonate crystals crystals
formed formed by
by carbonation;
carbonation; (b) XRD results
(b) XRD results of calcite. of calcite.

3.3.Results
Resultsand
andDiscussion
Discussion
Thewater
The watersample
samplehardness
hardnesslevels
levelswere
weremeasured
measuredby bythe
theEDTA
EDTAmethod
methodandandthe
thehardness
hardnesswas was
reduced by
reduced bythe
thecarbonation
carbonationprocess.
process. In
In addition,
addition, the
the pH
pH levels
levels before
before and
andafter
aftercarbonation
carbonation were
were
measured in all of the water samples. During the carbonation process the CO 2 injection, temperature
measured in all of the water samples. During the carbonation process the CO2 injection, temperature
and pH
and pH effect
effect played
playedaakeykeyrole to precipitate
role the the
to precipitate Ca2+Ca
and2+ Mg
and carbonates
2+ and to reduce
Mg2+ carbonates and tothe hardness
reduce the
in different
hardness water samples.
in different Table 3 Table
water samples. shows3 shows
the hardness of different
the hardness waterwater
of different samples before
samples and after
before and
carbonation.
after carbonation.

Table3.3.Hardness
Table Hardnessof
ofdifferent
differentwater
watersamples
samplesbefore
beforeand
andafter
aftercarbonation.
carbonation.

Water Hardness-before Water Hardness after Carbonation (mg/L)

Sample Name Water Hardness-before Water Hardness after Carbonation (mg/L)
Sample Name Carbonation (ppm) 7 g/L CO2 for 3 min 14 g/L CO2 for 4 min 21 g/L CO2 for 5 min
Carbonation (ppm) 7 g/L CO for 3 minwater14 g/L CO2 for 4 min 21 g/L CO2 for 5 min
2
I. Artificial hard
A-(1) 38 I. Artificial
24 hard water 17 12
A-(2)A-(1) 84 38 52
24 17 39 12 22
A-(3)A-(2) 110 84 52
65 39 50 22 24
A-(3) 110 65 50 24
A-(4) 172 108 79 43
A-(4) 172 108 79 43
A-(5)A-(5) 344 344 210
210 158 158 90 90
II. Drinking water samples
II. Drinking water samples
D-(1) 96 60 45 32
D-(1) 96 60 45 32
D-(2)D-(2) 60 60 38
38 25 25 17 17
D-(3)D-(3) 22 22 14
14 10 10 7 7
D-(4)D-(4) 52 52 33
33 24 24 18 18
III.
III. Natural watersamples
Natural water samples
N-(1)N-(1) 64 64 40
40 30 30 19 19
N-(2)N-(2) 56 56 35
35 27 27 15 15
N-(3)N-(3) 64 64 40
40 29 29 18 18
N-(4) 70 45 32 14
N-(4) 70 45 32 14
N-(5) 132 79 52 20
N-(5)N-(6) 132 140 79
88 56 52 21 20
N-(6)N-(7) 140 76 88
50 35 56 16 21
N-(7)N-(8) 76 66 40
50 29 35 18 16
N-(8) 66 40 29 18
3.1. Effect of Carbon Dioxide Flow Rates
3.1. Effect of Carbon Dioxide Flow Rates
The carbonation process by the closed pressure reactor method was in an aqueous medium.
Theamounts
Different carbonation
of COprocess by the closed pressure reactor method was in an aqueous medium.
2 gas were injected into the reaction bottle for different reaction times, such as
Different amounts of CO 2 gas were injected into the reaction bottle for different reaction times, such
7 g CO2 per liter for 3 min reaction, 14 g CO2 per liter for 4 min reaction and 21 g CO2 per liter for
5asmin
7 greaction
CO2 pertimes.
liter for 3 mindioxide
Carbon reaction,was
14 g CO2 per
injected liter
into thefor 4 min reaction
reaction bottle as and 21 ginCO
shown 2 per liter for
Figure 4.
5 min reaction times. Carbon dioxide was injected into the reaction bottle as shown
The basic two steps involved in the carbonation reaction are (i) hydration of carbon dioxide in Figure 4. as
The basic two steps involved in the carbonation reaction are (i) hydration of carbon
shown in Formulas (1)–(3); (ii) the carbonate ions react with calcium ions to form calcium carbonate dioxide as
shown in Formulas
precipitates (Formula(1)–(3);
(4)). (ii) the carbonate ions react with calcium ions to form calcium carbonate
precipitates (Formula (4)).
CO2(g) + H2O(l) ↔ H2CO3(aq)
(1)
(Dissociation of aqueous CO2 into water)
Water 2018, 10, 54 6 of 10

CO2(g) + H2 O(l) ↔ H2 CO3(aq)

(1)
(Dissociation of aqueous CO2 into water)

H2 CO3(aq) ↔ H+ + HCO3 − (2)

HCO3 − → H+ + CO3 2− (3)

(Produces supersaturation when)
(Ca2+ )(CO3 2− ) (4)
S1 = Ksp >1
(Formation of nuclei or critical cluster)
Ca2+ + CO3 2− → CaCO3 (nuclei)
(5)
(Crystal growth occurs spontaneously)

Ca2+ + CO3 2− → CaCO3 (Calcite)

(6)
(Finally, calcite formed)
Carbon dioxide species are important participants in reactions that control the pH of natural
waters. Reactions among the alkalinity-related species, aqueous CO2 , H2 CO3 (aq), HCO3 − , and CO3 2− ,
and directly pH related species, OH− and H+ , are relatively fast and can be evaluated with chemical
equilibrium models. Rates of equilibration between solute species and gaseous CO2 across a phase
boundary are slower, and water bodies exposed to the atmosphere may not be in equilibrium with it at
all times [11].
Here, we have presented the basic theory concept. The theory behind the calcium–carbon-dioxide
equilibrium states that when gas carbon dioxide is pressed into the water, this takes place according
to Henry’s law. The carbon dioxide combines with water and forms (diprotonic) carbonic acid,
which is very difficult to find analytically, and for this reason is presented as aqueous carbon dioxide
subsequently split into hydrogen ions and hydrogen carbonate ions. The hydrogen carbonate ion then
may release a hydrogen ion and also a carbonate ion.
The carbonate ions thus formed combine with calcium (and similarly magnesium) to form calcium
carbonate. This substance is difficult to dissolve in water and precipitates quite easily. The calcium
carbonate precipitates easier at increased water temperature. The equilibrium [Ca2+ ] + [CO3 2− ]
= [CaCO3 ] tells at which concentrations precipitation takes place. The unique character of calcium
carbonate is also present, namely that its precipitation increases with temperature instead of the opposite.
Normally, it is easier to dissolve substances at increased temperature, but with CaCO3 it is the opposite,
which explains the great practical interest paid to hardness on the heating of water in different kinds of
boilers in households and industry. Thus, hardness removal increases with temperature.
The equilibrium can be computed by [Ca2+ ] × [CO3 2− ] = Ks , where Ks is the
temperature-dependent solubility product for CaCO3 . As the aim is to remove the hardness, the actual
Ca content should be decreased. It means that the content of CO3 2- must increase in order to overcome
the solubility product and get a precipitation of CaCO3 . From the equilibrium, HCO3 − = H+ + CO3 2−
and the connected equation [H+ ] × [CO3 2− ] = K2 × [HCO3− ], where K2 is a temperature-dependent
constant, it follows that to increase the content of [CO3 2− ] it is necessary to increase the content
of hydrogen carbonate and/or decrease the content of [H+ ]. As – log [H+ ] = pH, meaning that an
increased pH gives more [CO3 2− ]. Thus, a higher pH is favorable for Ca precipitation.
There is a lowering of pH due to the dissociation of the carbonic acid into hydrogen ions and
hydrogen carbonate. However, the increase in hydrogen carbonate concentration also increases the
carbonate content, which contradicts the negative effect of a lower pH and creates a larger precipitation
of CaCO3 . CO2 hydration and complexes are possible with calcium ions and crystal formation.
The carbonation process by the closed pressure reactor method with different amounts of CO2
gas was injected into the reaction bottle for different reaction times, such as 7 g CO2 per liter for 3 min
Water 2018, 10, 54 7 of 10

reaction,
Water 2018, 1410,g 54
CO2 per liter for 4 min reaction and 21 g CO2 per liter for 5 min reaction times,7 of carbon
10
dioxide was injected into the reaction bottle as shown in Figure 4.
InInthis
thisstudy,
study,three
threedifferent
different water samples
sampleswere
wereused,
used,including
including (i)(i)
artificial hard
artificial water
hard samples,
water samples,
(ii)(ii)drinking
drinkingwater watersamples,
samples, and
and (iii)
(iii) natural
natural water
watersamples,
samples,totoreduce
reducehardness
hardness byby
thethe
carbonation
carbonation
process.The
process. Theresults
resultsclearly
clearlyindicated
indicatedthat
thatthe
thehardness
hardnessof ofthe
the different
different water
water samples
samples was
was reduced
reduced by
by approximately 30–40% using 7 g CO 2/L for 3 min carbonation, reduced by 50–60% using 14 g
approximately 30–40% using 7 g CO2 /L for 3 min carbonation, reduced by 50–60% using 14 g CO2 /L at
CO2/L
4 min at 4 min carbonation,
carbonation, and reduced andbyreduced
70–85% by 70–85%
using using
21 g CO 21 g CO2/L at 5 min carbonation at room
2 /L at 5 min carbonation at room temperature.
temperature.
However, the water hardness gradually decreased in different artificial (A), drinking (D) and
However, the water hardness gradually decreased in different artificial (A), drinking (D) and
natural (N) water samples with increasing CO2 gas flow rates from 7 g/L to 21 g/L at room temperature,
natural (N) water samples with increasing CO2 gas flow rates from 7 g/L to 21 g/L at room
as shown in Figure 6.
temperature, as shown in Figure 6.
When the CO2 pressure in the reactor increased, the bicarbonate and carbonate ions increased
When the CO2 pressure in the reactor increased, the bicarbonate and carbonate ions increased
due to the dissociation of carbonic acid, and these carbonate ions reacted with2+Ca2+ and2+Mg2+ ions
due to the dissociation of carbonic acid, and these carbonate ions reacted with Ca and Mg ions to
toincrease
increasethe thehardness
hardness removal
removal efficiency.
efficiency. Bicarbonate
Bicarbonate and carbonate
and carbonate ionsincreased
ions was was increased
due to due
the to
the dissociation of carbonic 2+ 2+
dissociation of carbonic acid,acid, and these
and these carbonate
carbonate ions reacted
ions reacted with Cawith
2+ andCaMg2+ and
ions Mg
and to ions and to
increase
increase the hardness removal efficiency at a lower pH of 4–6
the hardness removal efficiency at a lower pH of 4–6 for 5 min reaction time. for 5 min reaction time.

Figure 6. Reducing water hardness by carbonation in different water (a) artificial water; (b) drinking
Figure 6. Reducing water hardness by carbonation in different water (a) artificial water; (b) drinking
water; and (c) natural water samples.
water; and (c) natural water samples.

3.2. Effect of Temperature

3.2. Effect of Temperature
The five different artificial hard water samples were tested for reducing hardness with different
The five different
temperatures: 25, 40 andartificial hardresults
60 °C. The waterclearly
samples were tested
indicated forhardness
that the reducingremoval
hardness with different
efficiency was
temperatures: 25, 40 and 60 ◦ C. The results clearly indicated that the hardness removal efficiency
enhanced up to 60–70% by the carbonation process with 21 g of CO2/L for 5 min reaction at 40 °C
was enhancedand
temperature up 80–85%
to 60–70% by the
hardness wascarbonation
reduced byprocess withprocess
carbonation 21 g ofwith
CO221 /Lg for
of CO5 min reaction
2/L for 5 min at
◦ C temperature and 80–85% hardness was reduced by carbonation process with 21 g of CO /L for
40reaction at 60 °C temperature. These results clearly indicated that the water hardness gradually 2
5 min reaction
decreased with 60 ◦ C temperature.
at increasing temperatureThese
dueresults clearly indicated
to the reduction thatMg
of Ca2+ and the2+ water
ions inhardness gradually
the carbonation
process, as
decreased shown
with in Figure
increasing 7.
temperature due to the reduction of Ca2+ and Mg2+ ions in the carbonation
process, as shown in Figure 7.
Water 2018, 10, 54 8 of 10
Water 2018, 10, 54 8 of 10

Water 2018, 10, 54 8 of 10

Figure 7. Water hardness reduced by carbonation at different temperatures in artificial hard water
Figure 7. Water hardness reduced by carbonation at different temperatures in artificial hard
samples.
water samples.
Figure 7. Water hardness reduced by carbonation at different temperatures in artificial hard water
The hardness removal studies were conducted at different temperatures of 25, 40, and 60 °C.
samples.
The hardness removal ◦
Temperature plays a majorstudies were
role in the conducted
removal at different
of metal ions in the temperatures
water. Figureof7 25, 40, and
reveals that 60
the C.
Temperature
removalThe plays
hardness
of hardness a major
removal role
increases intemperature
thewere
studies
as removal of metal
conducted ionsmay
at different
increases, this intemperatures
the water.
partly be dueFigure
ofto25, 7 increase
the40,reveals that
°C.ionthe
and 60 in
removal
mobilityof hardness
Temperature
for theplays
COincreases
2a major as temperature
role increases,
in the Temperature
gas molecules. removal of metal this
ions may
affects in the
the partly
water.be due
Figure
interaction to the the
7 reveals
between increase
that 2 in
COthe gasion
removal
mobility
molecules of hardness
for the
and COthe
2 gas increases
molecules.
metal ions, as temperature
Temperature
which increases,
influences affects
the this
the may partly
interaction
stability of the be due
between
metal-COto the
the
2 increase
CO
gas gas in
complex.
2 ion
molecules
The
and mobility
the metalfor
carbonation of the
ions, CO2 gas
calcium
which ionsmolecules.
influences the Temperature
proceeds at temperatures
stability affects
of the the interaction
over
metal-CO 252 gas between
°C, complex.
while theThe thecarbonation
CO2 gas of of
carbonation
molecules
magnesium
calcium and the
ions should
ions proceeds metal ions, which
be possible only
at temperatures influences
overat25 ◦
higher the stability
temperatures.
C, while of the metal-CO 2 gas complex. The
the carbonation of magnesium ions should be
carbonation of calcium ions proceeds at temperatures over 25 °C, while the carbonation of
possible only at higher temperatures.
3.3.magnesium
pH Effects ofions should be possible only at higher temperatures.
Carbonation
3.3. pH The
Effects
pHofofCarbonation
all samples was measured before and after carbonation. The CO2 gas molecules react
3.3. pH Effects of Carbonation
with
Thewater-producing
pH carbonic acid and the pH is lowered, see Figure 8,The
where it alsomolecules
is found that
The of
pHall
ofsamples was
all samples measured
was measuredbefore
before and aftercarbonation.
and after carbonation.The COCO 2 gas
2 gas molecules react react
at higher
with CO2 flow rates
water-producing the pH
carbonic becomes
acid lower.
and the pH is lowered, see Figure 8, where it also is found that at
with water-producing carbonic acid and the pH is lowered, see Figure 8, where it also is found that
higher
at CO 2 flow
higher CO2rates
flow the
ratespH
thebecomes lower.
pH becomes lower.

Figure 8. pH
Figure changes
8. pH inindifferent
changes differenthard
hardwater
water samples, (a) artificial
samples, (a) artificialhard
hardwater,
water,(b)
(b)drinking
drinking water
water and
and
Figure 8. pH changes in different hard water samples, (a) artificial hard water, (b) drinking water and
(c) (c)
natural water
natural samples
water samplesby bycarbonation
carbonationat
at different CO22 flow
different CO rates. .
flowrates
(c) natural water samples by carbonation at different CO2 flow rates.
Water 2018, 10, 54 9 of 10
Water 2018, 10, 54 9 of 10
Water 2018, 10, 54 9 of 10

3.4.
3.4. Water
Water Hardness
Hardness Removal Efficiency of
Removal Efficiency of the
the Carbonation
Carbonation Process
Process
The hardness removal
The hardness removal efficiency
efficiency was
was 70–80%
70–80% for
for artificial
artificial water
water samples,
samples, 60–70%
60–70% for
for drinking
drinking
water samples and 70–85% for natural water samples, respectively. The results are shown in
water samples and 70–85%
70–85% for
for natural
natural water
water samples,
samples,respectively.
respectively.The
The results
resultsare
areshown
shownininFigure
Figure9.
Figure 9.9.

Figure
Figure 9.
9. Water
Water hardness
hardness removal
removal efficiency
removal efficiency of
efficiency of the
of the carbonation
the carbonation process.
carbonation process.
process.

3.5.
3.5. Crystal Growth Mechanism
Mechanism
3.5. Crystal Growth Mechanism
In the
In the carbonation
thecarbonation
carbonation reaction,
reaction, the CO
CO2was
the2 gas gas was
2 gas was hydrated
hydrated and formed
formed negatively
andnegatively negatively charged
charged
In reaction, the CO hydrated and formed charged bicarbonate
bicarbonate
bicarbonate ions. Under super-saturated conditions2+ the Ca 2+ and Mg2+ nucleated and formed calcium
2+
ions. Underions. Under super-saturated
super-saturated conditionsconditions
the Ca the andCa
Mgandnucleated
2+ Mg nucleated
2+ and formed
and formed calcium
calcium and
and
and magnesium
magnesium carbonates
carbonates [12,13].
[12,13]. Consequently,
Consequently, small
small calcite
calcite crystallites
crystallites appeared
appeared on
on the
the surface,
surface,
magnesium carbonates [12,13]. Consequently, small calcite crystallites appeared on the
as shown
shown in in Figure
in Figure 10,
Figure 10, which
10, which presents
which presents the
presents the crystal
the crystal growth
crystalgrowth mechanism
growthmechanism
mechanismof of the
ofthe carbonation
thecarbonation process.
carbonationprocess.
process.
as shown

Figure 10. Crystal growth mechanism of the carbonation process with closed pressure reactor
reactor..
Figure
Figure10.
10.Crystal
Crystalgrowth
growthmechanism
mechanismofofthe
thecarbonation
carbonationprocess withclosed
processwith closed pressure
pressure reactor.

4.
4. Conclusions
Conclusions
4. Conclusions
The purpose
purposeofof
The purpose this
ofthis
this experimental
experimental study
study was to
to determine the
the hardness of
of different water
The experimental study was was determine
to determine the hardness hardness
of different different water
water samples
samples
samples collected
collected from
from different
different areas
areas in
in South
South Korea,
Korea, and
and to
to reduce
reduce the
the hardness
hardness by
by a
a simple
simple
collected from different areas in South Korea, and to reduce the hardness by a simple carbonation
carbonation
carbonation process
process in
in aa closed
closed pressure
pressure reactor.
reactor.
process in a closed pressure reactor.
(i)
(i) The
The carbonation
carbonation process
process effectively
effectively reduced
reduced the
the hardness
hardness inin all
all artificial
artificial water
water samples
samples by by
(i) approximately
The carbonation process
(70–80%). effectively
At room reduced
temperature, the
a 21hardness
g/L CO in all artificial water samples
2 flow rate for 5 min was enough to
by
approximately (70–80%). At room temperature, a 21 g/L CO2 flow rate for 5 min was enough to
approximatelyof(70–80%).
remove At room 2+ temperature, a 21 g/LThe
CO2 flow ratereduction
for 5 min was enough to
remove most
most of thethe Ca
2+ and
2+ and Mg
Ca2+ Mg2+2+ions
ions from
from the
the water.
water. The hardness
hardness reduction increased
increased with
with
remove
increasingmost of the Ca and Mg ions from the water. The hardness reduction increased with
increasing temperature,
temperature, because
because carbon
carbon dioxide
dioxide effectively
effectively reacts
reacts with
with Ca Ca2+2+ and
and Mg
2+ 2+ ions with
Mg2+2+ ions with
increasing
increasing temperature, because carbon dioxide effectively reacts with Ca and Mg ions with
increasing temperature. The results indicated that 85% of the hardness was possible to
temperature. The results indicated that 85% of the hardness was possible to remove
remove
by
by aa simple
simple carbonation
carbonation method.
method.
Water 2018, 10, 54 10 of 10

increasing temperature. The results indicated that 85% of the hardness was possible to remove by
a simple carbonation method.
(ii) In drinking water samples the hardness was also reduced effectively using the carbonation
process, with 21 g/L CO2 at room temperature for 5 min reaction reducing the water sample
hardness by approximately 60 to 70%.
(iii) For the natural water samples collected from different areas of South Korea, 21 g/L of CO2
carbonation for 5 min at room temperature reduced the hardness by 70 to 85%. The results
revealed that the carbonation process in a closed pressure reactor effectively control the water
hardness of different kinds of water by relatively simple means.

Acknowledgments: This research was supported by a research grant of the “Research and Education Program”,
Chemical Engineering Department, Kwangwoon University, Seoul, Korea.
Author Contributions: Min Kyung Ahn collected the water samples from various places and performed
the experiments. Choon Han, Ramakrishna Chilakala and Thriveni Thenepalli conceived and designed the
experiments; analyzed the data and wrote the manuscript.
Conflicts of Interest: The authors declare no conflict of interest.

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